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P
Id ORNL-3391
CHEMISTRY DIVISION
M. A. Bredig
4’
i
u a-
! c
iii
CONTENTS
i
-
Page
Abstract.......................................................... 1
Introduction...................................................... 1
"Metallic" Metal Solutions........................................ 4
Alkali-Metal-Alkali-Halide Systems.. ......................... 4
Phase Diagrams. ......................................... 4
Physical Properties..................................... 13
Alkaline-Earth-Metal-Halide Systems.. ........................ 23
Phase Diagrams. ......................................... 23
Electrical Conductance.................................. 29
Rare-Earth-Metal-Trihalide Systems. .......................... 30
Phase Diagrams.... ...................................... 32
Electrical Conductivity.. ............................... 37
"Nonmetallic" Metal Solutions..................................... 41
Transition Metals............................................ 43
Posttransition Metals........................................ 44
' ^
S~aly. ..................................................... 51
References................................................... 52
L
,
MIXTURES OF METALS WITH MOLTEN SALTS
M. A. Bredig
INTRODUCTION
1
F'
2
Alkali-Metal-Alkali- H a l i de Systems
Phase Diagrams
0
L, ,
le c 1 C
UNCLASSIFIED
ORNL-LR-WG. 2 t 8 9 4 A
4 200 1200
I I I I I I I I I ' 0
X
COOLING CURVES,THIS WORK
EQUILIBRATION MAB JWJ WTS
HIGH TEMPERATURE RANGE A EOUILIBRATION', H R ~ ~. e '
UNCLASSIFIED
ORNL-LR-DWG 214 DlUM METAL-SODIUM HALIt
SYSTEMS
900
TWO LIQUIDS
900 900
050
800 800
600
4400 c
I
ONE L I Q U I D
(026'
ONE L i a u i ~
600
4400 Ln
I
10
I
20
I
30
t
40
I I
50 60
mole % K
I
70
I
80
Ml
90 700
-006
t SOLID SALT+ LIQUID METAL
.I .2 .3 .4 .5 .6 .7 .8 .9
N
.I .h .:.k .k ;.
656'
SOLI~SALT+LIOUID
;.
METAL
.b .A 6oo
MOLE %SODIUM M E T A L MOLE FRACTION OF METAL+ MOLE FRACTION OF METAL+
Fig. 1. Potassium Metal-Potassiur n
Halide Systems [J. W. Johnson and M. Fig. 2. Sodium Metal-Sodium Halide Systems, Fig. 3. Sodium Metal-Sodium Halide Systems [M.
A. Bredig, J . P h y s . Chem. 62, 606 (1958) High-Temperature Range [adapted from M. A. A. Bredig and H. R. Bronstein, J . P h y s . Chem. 64,
(reprinted by permission of the copyright Bredig and H. R. Bronstein, J. P h y s . Chem. 65 (1960) (reprintedby permission of the copyright
owner, the American Chemical Society)]. 64, 64 (1960)l. owner, the American Chemical Society)l.
UNCLASSIFIED
ORNL-LR-DW. 34067A
, I I
UNCLASSIFIED
ORNL-lLR-OWG.370
800 I
UNCLASSIFIED
ORNL-LR-DWG. 32909A
MOLE % M E T A L
MOLE X METAL
Fig. 4. Alkali Metal-Alkali Metal
Fluoride Systems [A. S. Dworkin, H. Fig. 5. Cesium Metal-Cesium
R. Bronstein, and M. A. Bredig, 1. Halide Systems [adapted from M. A.
P h y s . Chem. 66, 572 (1962) (reprinted Bredig, H. R. Bronstein, and W. T.
by permission of the copyright owner, Smith, Jr., J. Am. Chem. SOC. 77,
the American Chemical Society)]. 1454 ( 1955)l.
Table 1 Principal Data for Alkali-Metal-Alkali-Halide Phase Diagrams
Monotectic
sat-
Consolute
Metal Salt Tap Phase Comp. (mole $ M) Eutectic Metal
system Compa
MX-M
(m)
(?): (OK) Salt-Rich Metal-
Rich
Temp
(OK)
Comp
(mole $ M) (mole m) (‘E)
Solid Liquid Liquid
LiF 1121 n20 lb 3 1603 40 452
LiCl 883 882b 0.5b 452
LiBr 823 822b 452
LiI 742 741b lb 452
NaF 1268 1263 3b 83 1453 28 10-9 370
NaCl 1073 1068 0.15 2.1 97.7 l353 50 370
NaBr 1020 103.3 0.15 2.9 96.6 1299 52 370
NaI 933 930 1.6 98.6 l306 59 370
KF ll31 1122 4.9 51.7 1177 20 3 x 10-4 337
KC1 1043 1024 0.04C 10.5 75 .o 1063 39 10-9 337
KBr 1007 981 0 .03c 19.o 69.2 1001 44 10-9 337
KI 954 931 13.5 82.5 990 50 10-9 337
RbF 1068 1046 9b 40b 1063 21b 312
RbCl 995 969 18 57 979 37 312
RbBr 965 a a d d globre ub,e 312
RbI 920 888 22 73 907 51 312
CsF 976 d d d d d d 10-3 302
CSCl 918 d d d d d d 10-8 302
CsBr 909 d,a d,a d,a d,a d,a d,a 10-7 302
CSI 899 d d d d d d 10-7 302
%stimate by extrapolation.
bEstimated.
C
By extrapolation from ref 13.
%o miscibility gap.
e
Unstable.
8
UNCLASSIFIED
ORNL-LR-WIG. 6707
800
1 F
700 I
600
0
i
I I
4
I t
R
8
I
Rb
' I
42
- (cm3 mole-')
' I
46
'
UNCLASSIFIED
ORNL- LR-DWG. 701
5000 I I I I I I I I I
4000
d
- 3000
-
c
0
%
s - I
-
c
L
t
k 2000
4000
- I
11
M(1iquid) +* M(gas) ,
M(gas) -+ in d i l u t e solution) .
The first s t e p i s simply t h e vaporization of the metal f o r which data are
available.23 The thermodynamics r e l a t e d t o t h e second step, which i s t h e
dissolution of t h e gas molecules, i s discussed elsewhere.24 The i n f l u -
ence of the f i r s t s t e p may be i l l u s t r a t e d by the r e l a t i v e values of RT
In p given i n Table 2, where p i s the p a r t i a l pressure of the metal mono-
mer i n t h e vapor i n atmospheres. Aside from differences i n t h e second
process, the influence of the vaporization s t e p would tend toward an in-
creasing r e l a t i v e s o l u b i l i t y of metal i n salts i n the order of increasing
vapor pressure, L i < Na < K < Rb < C s .
Where Henry's law applies, t h e second process i s b e s t described i n
terms of the Henry's law constant, %,
RT ~n
I
p monomer)
(kcal mole)
( a t looo'~)
Metal bp
(OK)
Range of Values of Tc
(OK)
Physical Properties
UNCLASSIFIE0
ORNL-LR-DWG. 23048A
6P '845'
-
2l
NO NoCl
Na-NaBr
2-
0 2I I 4l ~6 l 8~ 0l ,2 l 4, l 6, 8l , 4l ,
0 l , ~ o
SODIUM METAL (mole %) POTASSIUM METAL (mole %)
UNCLASSIFIED
ORNL-LR- DWG.54649
I I I I I I
J
Fig. 10. Specific Conductivity of Solutions of
Sodium Metal in Sodium iodide [H. R. Bronsteiii and
M. A. Bredig, J . P h y s . Chem. 65, 1221 (1961) (re-
printed by permission of the copyright owner, the
American Chemical Society)].
0
I I
2
I
4 6
I I I
S i 0 4 2
I
4
MOLE PER CENT SODIUM METAL
UNCLASSIFIED
ORNL-LR-DWG. 54650
48 - -
46 - -
-
s
0
- 42- -
-
a
2
-
I I I I I
0 2 4 6 8 4 0 4 2
Ir' where Asoh are t h e equivalent conductances of t h e solution
and
and salt, and NM i s t h e equivalent f r a c t i o n of metal. The term % repre-
sents t h e change of t h e conductance caused by t h e addition of one equiva-
l e n t of m e t a l t o an mount of salt contained i n t h e solution of t h e given
composition which i s between two electrode plates 1 cm apart.
i Figures 1 2 and 13 show, i n a more s t r i k i n g form than Figs. 9, 10, and
11, t h e t y p i c a l difference i n the behavior of sodium and potassium. While
i n t h e potassium systems t h e apparent equivalent conductance of t h e metal
solute, %, -
rises monotonically and with increased r a t e with increasing
m e t a l content, it -
drops rapidly i n t h e sodium solutions toward a minirmun,
which obviously would be followed by a rise i f greater s o l u b i l i t y would
permit higher concentrations of metal t o be dissolved.
These c h a r a c t e r i s t i c changes of % w i t h m e t a l concentration m y be
interpreted as follows: A t i n f i n i t e dilution of the m e t a l , i n both the
sodium and potassium solutions, electrons are i n a s t a t e i n which they
can contribute t o the carrying of current. Rice,29 assuming a "random
walk" of t h e electrons, has performed t h e o r e t i c a l calculations f o r this
s t a t e a t infinite dilution which are correct within an order of magnitude
of t h e observed conductivity. For t h e potassium solutions, Rice's theory
predicts an increase of & w i t h m e t a l concentration. Bronstein and Bredig
suggest t h a t electron o r b i t a l overlap plays a r o l e i n this increase, and
doubtlessly this becomes important a t higher m e t a l concentrations. How-
ever, i n t h e sodium solutions, another important factor appears t o be
present t h a t actually removes electrons from t h e conduction process with
increasing m e t a l concentration. The trapping of electrons i n pairs t o
form diatomic molecules of Na2 was suggested27 t o r a t i o n a l i z e this dif-
ference. !The f a c t t h a t Na2 i s r e l a t i v e l y more stable i n t h e vapor than
i
K2 (the heats of dissociation are 17.5 and 11.8 kcal/mole respectively)
suggests t h a t this i s reasonable. Measurements a t higher temperature i n
t h e sodium-Fontaining systems, i f t h i s hypothesis were true, would lead
t o behavior more l i k e the potassium-containing systems because of t h e
greater dissociation of Na2. In t h e l i t h i u m systems a s t i l l greater de-
gree of pairing should occur. This, r a t h e r than a short relaxation time,30
iw
i
might be t h e reason f o r t h e absence of electron spin resonance i n solutions
of lithium i n molten lithium iodide.
18
UNCLASSIFIED
ORNL-LR-OWG 23047A
-
c)
1
40-
No in NH3
0
T
- at -335'
a -
CT
0 2 4 6 0 40 42 44
METAL (mole %)
20
Crystal Radius e1 Br I
of cation (A)
Na 0.95 6000
. . . . . . . . . . . . . . . . . e
(820O C )
....
(870OC)
b e
%stimated.
4 5 6
REDUCED TEMPERATURE, r/e
Fig. 14. Electron Mobility in Alkali Halide Crystals
[A. Smakula, Nu&. Ges. Wiss. GBttingen, 11 1(4), 55
(1934)l.
21
Phase Diagrams
1
I
I
I
I
I:
700 - " 0
a+#
0 0 0 n n
(I + L,'
Y,
-
I I I I I I I I I I I
0 40 20 30 40 50 60 70 80 90 f00
BaClp MOLE PER CENT Ea Ea
a
Considerable metal s o l u b i l i t y i n ( f l u o r i t e type o f ) s o l i d i s l i k e l y .
bSee r e f 46.
C
Considerable metal s o l u b i l i t y i n high-temperature c r y s t a l form of BaCl2 ( f l u o r i t e type ?) is
likely .
iu UNCLASSIFIED
ORNL-LR-DWG. 70746
I
I
0 50 4 00
COMPOSITION ( mole % Ca 1
- N2 (Solid)]
would leave t h e p o s s i b i l i t y open f o r a cryoscopic n l a r g e r than 1,
possibly 2, a t low m e t a l concentration. T h i s cryoscopic n = 2 would be
i n agreement with t h e findings i n t h e corresponding chloride system,
CaCl2-Ca, where Dworkin, Bronstein, and Bredigso found n a l s o t o be only
s l i g h t l y less than 2. Here, however, no s o l i d solution was assumed, the
c r y s t a l s t r u c t u r e being quite different, with s i x f o l d r a t h e r than eight-
f o l d coordination of anions around cations. I n both cases the reaction
would then seem t o be Ca + Ca2+ + 2e-, as also suggested by t h e elec-
I
U t r i c a l conductivity (discussed below), with a possible, though much l e s s
?i
28
Tm -T -- m
N
N-43
= ll00"C (observed e~perimentally~l) ,
N2(J) - N2(C) i l l 2 0.04
Lsm m
n=-
RT
x--
LJI2
N
4xlloo
2 X 1233
2 1.8 N" 2 .
Again, a solution mechanism corresponding either to Ba + Ba2+ + 2e-
and/or (less likely) Ba + Ba2+ + 2Ba+ seems indicated by these experi-
men-bal data. On the basis of activity measurements carried out by equi-
libration of MgC12 with MgAl alloys of known activity, Rogers, Todinson,
and Richardson45 suggest for Mg-MgC12 the solution mechanism Mg + Mg2+ +
E l e c t r i c a l Conductance
W
Dworkin, Bronstein, and Bredig50,52’53 found it impossible t o apply
the method used f o r measuring conductivity i n t h e alkali-metal systems t o
t h e alkaline-earth systems. While the components, molten salt o r l i q u i d
metal, were found singly not t o react extensively, i f a t all, with t h e
synthetic sapphire c e l l , t h e i r mixtures d i d attack t h e l a t t e r readily.
Recourse w a s taken t o an all-molybdenum-metal apparatus embodying an as-
sembly of two p a r a l l e l rods as electrodes which were immersed i n t o t h e
melt from above t o a varying, accurately determined depth. With pure
molten salts the low resistance of t h i s c e l l l e d t o large e f f e c t s due t o
electrochemical polarization of t h e electrodes and resulted i n a large
frequency dependence of t h e measured resistance which could not be ex-
trapolated t o i n f i n i t e l y high frequency with any accuracy a t a l l . How-
ever, the addition of even small amounts of metal, acting as a depolar-
izer, removed t h e frequency dependence. Thus, it w a s possible t o use t h e
apparatus with t h e metal solutions and t o c a l i b r a t e it with solutions of
cadmium i n cadmium chloride. The specific conductivity of these solu-
t i o n s i s known from the early measurements of Aten i n 1910 (ref 5 4 ) and
was confirmed by new measurements with the sapphire cell.53
Only results f o r solutions of calcium and strontium i n t h e i r diha-
l i d e s , excepting t h e fluoride, have been reported thus far.46*50 It was
concluded, as far as the limited data permit, t h a t calcium behaves some-
w h a t l i k e sodium i n t h a t the rate of increase i n s p e c i f i c conductivity
,
w i t h m e t a l concentration decreases (Fig. 18). The same i s true f o r
: .
strontium i n SrBr2 a t the r e l a t i v e l y low temperature of 7OO0C, but i n the
dichloride, a t 910°C, t h e behavior of strontium, giving a l i n e a r increase
of conductance with metal concentration, l i e s somewhere between t h a t of
sodium and potassium, with barium expected t o resemble t h e l a t t e r . The
decreasing equivalent conductance of the calcium-metal solute was a t t r i -
buted t o t h e formation, not of diatomic molecules, C a 2 , as with sodium,
but of hypothetical molecule ions, (Ca2)2+, i n which t h e t r a p f o r elec-
trons i s t h e single two-electron bond similar t o that i n Na2, or i n Cd2*+
and Hg22+.
30
UNCLASSIFIED
ORNL- LR- DWG.70122
4 .O
0
P I
I I
2
I
3
MOLE PER CENT METAL
Rare-Eaxth-MetalA’rihalide Systems
1131 11.5 470 2.4 9.0 1099 None None None None 1 2.o 1273 1193 ll87
1061 (ll.8)(e) 375 (2.4) 14.5 1001 None None None None 15.5 ll73 ll93
1052 (12.0) 490 (2.8) 8.2 1007 10231 None None 1103c 33 ll.73 1193 ll73
1090 11.7 4.80 2.6 9.0 1050 None None None None 9 1173 1068
1005 (U.8) 345 (2.0) 12 .o 960 None None None None 14 1173 1068
1034 12.o 460 2.7 8.8 988 1004i None .None 10811 32 1173 1068 1064
1059 ll.4 565 3 .O 17.0 919 None 9321 None None 19 1073 1208
966 (12.0) 545 3.4 16 .O 852 8741 None None None 18 1023 1208
loll 12.6 500 3.1 11.9 939 946c None None 10311 29 1073 1208 1180
1032 ll.6 590 3.3 14.0 9W None 9533. 9751 11141 31 1173 1297
955 (12.0) 1297
1060 9.2 740 3.2 26.5 764 None None None 835C 37 1073 1297
1204 (12 ?) 555 (2.8 ?) 14.0 1098 None None None 11041 14 ll73 1585
1270 (10 ? ) 390 (1.5 ? ? ) 12.0 1221 None None None None 15 1423 1782
(d)see r e f U.
(e)Figures i n parentheses are estimates.
32
Phase Diagram
UNCLASSIFIED
O R N L - LR-DWG. 70745
400 I I I I I I I I
-
- 90
0
W
K
3
I-
a
K
W
n
3 801
0
THERMAL ANALYSIS
O
701 I I I I I I I I I 1
IO 20 30 40 50 60 70 80 90 (00
MOLE PER CENT L a
34
UNCLASSI FIE0
ORNL-LA-DWG. 56015
g
w* t
UNCLASSIFIED
ORNL- LR-DWG. 56816
MOLE%Nd IN NdIs G.
-..
UNCLASSIFIED
ORNL-LR-DW$. 70759
I I I I I I I IQ I I
880 - -
+ T H E R M A L ANALYSIS ::Tr
860 - 0 EQUILIBRATION l! 7
3
X LITERATURE I
840 - 0
*+-+-' -
- 820- +-
-
+
P
w 800-
(r
3
760-
I = 740 -
720 - L aI -
L0I2.q2 2.00
1
!
-
7000 d, A 4; tk Lb 214 '28 22' 26 "'916 (00
UNCLASSIFIED
ORNL- L R - DWG. 70758
820 I I I I I I I / I I I '4
+ T H E R M A L ANALYSIS
0 EQUILIBRATION
780 X LITERATURE
++ +
640
I I I I I I I I I I "
0 4 8 42 16 20 24 28 32 36 40 700
PrI, MOLE PER CENT Pr I N Pr13 Pr
c
37
E l e c t r i c a l Conductivity
UNCLASSIFIED
ORNL- LR -DWG. 70425
-E
-
‘E
r
0
5 (0 45 20 25 30
MOLE PER CENT METAL
38
UNCLASSIFIED
ORNL-LR-DWG.70123
I
10
I
I
- 9 I
I
Fig. 25. Specific Conductivity in Rare
Earth Metal-Rare Earth Metal Iodide Systems
[R. A. Sallach et al., 1. Phys. Chern., in press
(1963) (reprinted by permission of the copyright
owner, the American Chemical Society)].
a
-.-
0 5 (0 15 20 25 30 35
I MOLE PER CENT METAL
39
6
Fig. 26. Electronic Conductance in Some Metal-Metal
Chloride Systems. Left: Eq uivalent Conductance of Metal
vs Mole Fraction of Metal. Right: Electronic Contribution
to Equivalent Conductance of Solution vs Product of Elec-
tron and Cation Concentrations [M. A. Brkdig, J. Chem.
Phys. 37, 914 (1962) (reprinted by permission of the copy-
right owner, the American Institute of Physics)].
UNCLASSIFIED
ORNL-LR-DWG. 66931
6-
I
a04
I I
0.08
I I
0.42
,
0.46
V I I I I I
0.04 0.02 a03 a04
-
N i NiCl2 9.1 977 None 70 In-InC1 InC1, In31nC16
"1n~12"
97
( I N C h
Ag-AgC1 0.03 490 None 71 TI.-T1C1 0.09 550 TlCl n
0.06 700 0.09 650 (TlAlC14?)
m-mc4 0.18 500 None 80 Sn-SnC12 0.0032 500 71
1.64 600
zn-znI2 0.28 500 None 80 Sn-SnBrz 0.068 500 71
1.65 670
c a-C a c l 2 14.0 550 None 54,79 Pb-PbCl2 0.020 600 71
21.0 800 0 -052 700
30 .O 1000 0.123 800
C d- C dBr2 14.0 550 None 79 Pb-PbI2 0 0024 4-40
20 .o 700 0.15 600
28 .O 900 0.41 700
Cd-CdIz 2.5 400 None 79 Sb-SbCl3 0.018 270 80
15 .O 700
25 .O 950 ~b-sb13 1.69 200 a214 80, 102
3.5 300
Hg-HgC12 7.0 280 Hg2 c12 73 5.8 400
18.0 4.00
4.0 .O 500 Bi-BiC13 28.0 202 107
46 00 320 "BiCl"
Hg-Hgl2 25 .O 230 Hg2 I 2 76 28 .O
35 .o 280 100.o
Ga-GapCl4 3.7 180 n Bi-BiBr3 21.0 205 108
57.0 294 "BiBr"
Ga-GazBrq 14.0 180 95 45 .O 4-40
10000 >538
80
Bi-BiI3 48.0 336 108
10000 #t58 "MI"
4
43
rapidly within each group with increasing atomic weight (see Table 6 ) . It
a l s o depends on t h e halide ion, and Corbett e t al. a t t r i b u t e t h i s l a t t e r
trend t o t h e r e l a t i v e tendency toward s t a b i l i z a t i o n of t h e higher oxida-
t i o n s t a t e by complexing with the halide ion, normally i n t h e sequence
C1 > B r > I, but reversed f o r C d and Hg.
Transition Metals
.
t h a t is, of electrons i n shallow, F-center-like traps, i s considered t h e
t h i r d , least l i k e l y p o s s i b i l i t y .
Posttransition Metals
UNCLASSIFIED
ORNL-LR-DWG. 56700
6001
600 I , 1 I I
I
: 5+L2
550 - I
I
RUFF 8 SCHMOER
SMITH 8 MENZIES
THIS WORK
QTHERMAL LJATA
AVISUAL DAm
MOLE PERCENT Hg
4.6
i
C d C l 2 lead t o t h e suggestion of i d e a l behavior f o r concentrations of
Cd2C12 i n CdC12 below approximately 2 mole $ Cd2C12, but increasing nega-
t i v e deviation from Raoult's l a w f o r CdC12 with increasing metal (Cd2Cl2)
solute concentration. This negative deviation (7 CdC12 = 0.96 o r 0.99
f o r a cadmium atom o r a C d 2 C l 2 solute, respectively) a t t h e monotectic
(15 mole C d 2 C 1 2 ) may be explained by the substitution of large cations
(Cd2)2+ f o r smaller Cd2+ ions. It i s analogous t o similar deviations
found i n systems with other l a r g e cations such as KCl-CdC12 and may or
may not be thought of i n terms of t h e formation of complex anions such as
(CdC14)2'.88 Perhaps t o explain t h e asymptotic decrease i n the negative
deviation with decreasing metal. concentration, t h e formation of undis- -
sociated species Cd4C16 and Cd3X4 has been suggested,79 but does not ap-
pear plausible i n a highly ionized and ionizing medium such as molten
CdC12. An alternative explanation i s t h a t i n s m a l l concentrations t h e
complex anion m a y a c t as a "common ion" w i t h respect t o some of the ions
i
Of t h e solvent salt, CdC12, or, i n other words, t h a t a c e r t a i n concentra-
t i o n of complex anions such as (CdC14)2' i s present, even i n pure molten
CdC12. Solid solution f o m t i o n which would invalidate any such i n t e r -
pretations of cryoscopic data i s deemed unlikely.
The observed negative deviation from Raoult's l a w would be more dif-
f i c u l t t o reconcile with t h e "physical" model (cadmium atoms), although
Nachtrieb86 points out that t h e t r u e s t a t e of affairs may be a subtle one,
perhaps corresponding t o a cadmium atom "solvated" by a Cd2+ ion82 o r t o
a solute species Cd22+ with an asymmetric charge distribution.
Observations by Grjotheim e t and by Hertzog and on t h e
e l e c t r i c a l transport of Cd with respect t o C1- were interpreted i n terms
of strong interaction between Cd and Cd2+. Other e f f e c t s such as those
produced by t h e addition of a t h i r d component upon the s o l u b i l i t y of
cadmium metal may be taken as an indication t h a t a fairly stable (Cd2)2+
ion exists. According t o Cubicciottigo t h e addition of KC1 t o CdC12 grad-
-
u a l l y lowers t h e s o l u b i l i t y of cadmium i n the m e l t . Corbett e t al.
explained this by assuming t h a t t h e excess chloride ions s t a b i l i z e the
higher oxidation s t a t e of cadmium by complexing. 80*88s 91 However, by
adding A l C l 3 (a strong Lewis acid) they prepared a solid, diamagnetic
compound of t h e formula Cd2(A1Cl4), containing a l l of t h e cadmium i n oxi-
dation s t a t e I.92 I n the melts t h e increased s t a b i l i t y of t h e cadmium(1)
47
i
oxidation state when the halide ion X 7 (Cl-, Br-, I-) i s replaced by the
l a r g e r AlX4' w a s considered t o r e s u l t from the decrease i n t h e i n t e r a c t i o n
of t h e Cd2+ cation with t h e anion, and, i n t h e solid, from t h e decrease i n
t h e difference i n l a t t i c e energies of t h e salts i n t h e two oxidation
states. The contrast between t h e dark-brown color of melts containing no
A l C l 3 and t h e light-green color of those i n which A l C l 4 - i s present was
a t t r i b u t e d t o the role, i n t h e former case, of t h e (highly polarizable!)
uncomplexed halide ion as a bridge i n a weak association between t h e ions
i n t h e two d i f f e r e n t oxidation s t a t e s , Cd22+ and Cd2+. Other examples of
deep color a r e found even i n aqueous systems containing Fe, Sn, Sb, o r Cu
i n two valence states.93
. I n the zinc systems t h e s o l u b i l i t y of t h e metal does not much exceed
1 mole $.80 Because of t h e strong halide complexing tendency of !Zn2+, it
i s doubtrul whether addition of A l X 3 would r a i s e the s o l u b i l i t y of zinc
i n znX2 t o any considerable extent by allowing t h e lower valence s t a t e
t o+form
(~n~~ ? ) i n greater concentrations.
I n the t h i r d B subgroup of the periodic system t h e halides of mono-
valent indium and thallium have long been known, and some of those of gal-
l i u m have a l s o been prepared recently.9698 "Dihalides" of these elements
have been recognized as ionic salts of t h e monovalent metal with anionic
complexes of t h e t r i v a l e n t metal, f o r example, Ga(I)[Ga(III)C14] .99-101
-
Again, A l C 1 3 was employed by Corbett e t a1.91994995998 t o a i d i n the cam-
p l e t i o n of t h e reaction 2Ga -t Ga3+ 3 3Ga+, t h a t is, t o convert a l l of t h e
gallium i n t o t h e low oxidation state (I), as i n Ga(I)AlC14.91 The solu-
! b i l i t y of aluminum m e t a l i n molten A l 1 3 w a s reported71 t o be as high as
0.3 mole $ a t 423OC.
I n t h e fourth group of posttransition elements, dihalides of germa-
nium as w e l l as those of t i n and l e a d a r e w e l l known stable compounds.
The s o l u b i l i t i e s of the l a t t e r metals i n t h e molten dihalides are very
small, 719 go and it does not seem t o have been shown as yet t h a t addition
of Al.C13 increases t h e solubility, although this would seem t o be a t e s t
f o r t h e existence of an oxidation s t a t e lower than 11.
A l l t h r e e elements of t h e f i f t h posttransition group, arsenic, anti-
mony, and bismuth, possess a very s t a b l e oxidation s t a t e (111). The
s o l u b i l i t y of t h e m e t a l i n t h e molten t r i h a l i d e s r i s e s rapidly with in-
!
! - creasing atomic number, and i n t h e bismuth systems even leads t o t h e for-
48
5 DECANTATION P
li~
! 49
! i
; u
!
form of oxidation s t a t e (I), namely, triangular (Bi3)3+, which they a l s o
f i n d i n the molten s t a t e t o represent the b e s t interpretation of radial
i
distribution f'unctions obtained by x-ray diffraction.
Various other studies have been made on t h e molten solutions of
bismuth m e t a l i n i t s t r i h a l i d e s Keneshea and Cubicciotti have meas-
ured t h e vapor pressures of BiX3 over these solutions1l6l6 and t h e i r
500
0
400
a
3
igf 300
E!
200
o-BlBr3+ BI Br
400
300
200
I I I
i a
a
100
W
! -
50
densities. 7*l1 7s While the chloride and bromide systems show large
positive deviation from Raoult's law for the solvent, BiX3, when atoms
are assumed to be the solute species, Bi13 seems to behave ideally up to
30 mole $ bismuth. The reasons for this peculiar behavior of the iodide
system are not apparent. Bredigflg interpreted the vapor pressure meas-
urements in the Bi-BiBr3 system in terms of an equilibrium between Biz
molecules, ions, and BiBr3, namely, 2Bi2 + ai3+ -+ 3(Bi~)~+,but
an equilibrium Biz + Bi3+ might explain these data equally
At higher temperatures the equilibrium appears to shift to Biz
and its dissociation products, Bi3+ and electrons. A multiple mechanism
for the dissolution of bismuth in BiC13 was also proposed by Mayer, Yosim,
and T0p01.109*120 Corbett121 suggested an interpretation of the same
vapor pressure data in terms of a tetramer, (BiC1)4, possibly with Bi-Bi
bonds to explain the diamagnetism of solid 1tBiC1."122 The diamagnetism
of the molten solutions was discussed by Nachtrieb.86 On the basis of emf
and polarographic measurements, Topol, Yosim, and O ~ t e r y o u n g pro-
~~~*~~~
pose the existence of an equilibrium nBiX eBinXn in both the chloride and
bromide systems, with n = 4 apparently given preference. An equilibrium
of this nature is also indicated by the optical absorption measurements
of Boston and Smith,125 in which the ratio of two optically distinct
species, probably the monomer and a polymer of Bi+, was shown to depend
on the bismuth-metal concentration. Thus, the majority of authors are
found to prefer the assumption of polymeric subhalide formation in solu-
tions of bismuth in the trihalides to that of bismuth atoms.7*117*118
The early measurements of the electrical conductance by Aten126*127 showed
a decrease in the equivalent conductivity of solutions with metal concen-
tration. This is much better understood in terms of subhalide and Biz
molecule formation than of dissolution of bismuth atoms.
The solubility of salts of several posttransition metals in the
liquid metals was dealt with by Yosim and Luchsinger.128 At sufficiently
high temperatures bismuth halides are completely miscible with bismuth
metal; Hg2C12 was found to be soluble in mercury metal to the extent of
7 mole $ at 60OOC. The solubility of PbC12 in lead at 1000° is given as
1 mole $, while the salts of the remaining metals are considered insoluble
in their metals. There appears to be no simple relationship governing
this behavior.
The question of specificity was also examined, that is, the question
of whether metals dissolve s a l t s other than their own halides. The solu-
51
SUMMARY
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c
59
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